Method for obtaining titanic oxid.



AUGUSTE J. ROSSI, O-F NIAGARA FALLS, NEW YORK, ASSIGNOR TO THE TITANIUM ALLOY MANUFACTURING COMPANY, OF NEW YORK, N. Y., A CORPORATION OF Patented May 23, 1916.

MAINE.

METHOD FOR OBTAINING TITANIC OXID.

1 184,131 Specification of Letters Patent.

No Drawing.

To all whom it may concern:

- Be it known that I, AUoUs'rE J. Rossr, a

citizen of the United States, and a resident of Niagara Falls, in the county of Niagara and State of 'New York, have invented cer tain new and useful Improvements in Methods for Obtaining Titanic Oxid, of which the following is a specification.

My present invention relates to procedures for obtaining titanic oxid as such from titaniferous ores in quantities suflicient for anted to me Letters Patent No. 905,232,

dated December 1, 1908, etc., it is desirable for some purposes, as for instance securing greatest possible electrical conductivlty n the copper product, that the titanium oxld employed in manufacture ofthe metallic ti-.

tanium required, should be as free as possible from associated substances likely to leave impurities such as silicates, or, more particularly, other metals such as iron in the resulting products.

Rutile ores are particularly desirable for titanium production for the purposes mentioned whenever procurable in suflicient quantity and of sufiicient purity at nonprohibitory prices. But even rutile, as it occurs in nature, is, in the mass, only more or less pure, being usually associated with more r less iron oxid, besides earthy bases such as alumina and magnesia, the latter mostly as aluminate of magnesia.

While in some ores, exceptionally rich in rutile, such gangue may not exceed 1% to 2% of the mass, in others it reaches as high as 15% or more; the latter, frequently designated as titaniferous iron, or ilmeno-rutile, ores, containing usually a predominance of iron oxid, much of which is associated with titanium oxid in the compound known as ilmenite, 2'. e. FeTiO or -FeO,TiO, and which, however unobjectionable for production of alloys of iron with titanir a, such as or its alloys, for which were- Application filed October 10, 1911. Serial No. 653,785.

by my U. s Letters Patent No. 609,466, dated August 23, 1898, renders such ores in the1r natural state unavailable for the special applications of titanium practically free from iron above referred to.

The ores containing the higher percentages of rutile have hithertobeen found segregated in quantities too small to be relied on for supply of industrial demands, as for mstance only in limited amounts in pockets of moderate content, or impregnating, in only low percentages, feldspathic or other rocks, concentration processes being required for separation of the rutile therefrom. On the other hand, titaniferous i. e. ilmenos rutile ores containing good percentages of titanic oxid, such as 35% to 40% or sometimes more, associated as aforesaid with large percentages of oxid of iron, say 50% to 55%, are found in vast deposits, procurable at a comparatively low cost, usually not exceeding that of ordinary iron ores.

The objects of my present invention comprise the separation or segregation of the titanium oxid as such from all classes of rutile-containing ores, but more particularly from the titaniferous iron, or ilmenorutile, ores above referred to, and the effecting of such separation or segregation by methods so economical and simple in operat1on as to insure, at a cost not prohibitory, supplies of titanium oxid sufficiently pure and in sufficient quantities to satisfy many industrial demands therefor.

I attain these objects by the following methods of treatment, viz. :-I first finely pulverize the particular rutile containing ore, such as titaniferous iron, or ilmenorutile, ore containing let us say up to 50% or even more of titanium oxid associated as aforesaid with more or less iron oxid, and thoroughly mix the resulting powder with .the now usually waste by-product resulting from present methods of manufacture of hydrochloric acid on industrial scales. This by-produ-ct, containing essentially bisulfate of soda associated with other more or less undesired substances, and hitherto usually neglected or thrown away as of insignificant utility for any industrial or other purposes, can now be obtained in requisite quantities at a comparatively insignificant price per ton. In making my said mixture I endeavor to proportion the amount of said by-product relatively to the ore treated in such manner as to supply to the titanic oxid and iron oxids of the ores suflicient bisulfate of soda to satisfy the respective chemical ailinities of the constituents of the substances mentioned for each other. I find in usual practies that a mixture of 1 part of ore to 2 or p 3 parts of the waste product referred to, which I may term for the purposes of this specific tion the bisulfate, are sufiicient for my treatment of average ores containing as high vas 4:0 to 50% of titanic oxid. It is obviously impossible to give to the manufacturer any hard and fast rule of proportion in this respect owing to the great variations existing in constituents of different ores, the object being to supply enough bisulfate of soda to insure the desired chemical combinations with constituents of the ferric and titanic oxids present. It is only necessary to ascertain these latter approximately and add the bisulfate accordingly, a

few of the operations to be next described being enough to indicate to those skilled in the art whether such addition is in excess or .depth. charged, the furnace is heated to a bright insufiicient, nor is it requisite for the success of my process that the bisulfate be added in exactly the amount required for the chemical reactions, both the cost of the bisulfate and its presence in reasonable excess being negligible. My said intimate mixture of ore and the bisulfate by-product mentioned I then charge onto thehearth of an open hearth furnace heated by direct coke fire in a grat'eor indirectly by producer gas. The hearth of the furnace or container should of course be constituted of, or lined with, materials sufi'iciently refractory to resist the action of the charge at the required temperature, to which end ,.aggloinerate(l magnesia and tar or agglomerated graphite may, for example, be employed as is done in open hearth furnaces. To avoid undesirable results from violent reactions in the charge, resulting from liberation of sulfuric acid, the hearth should be so shaped and the materials so arranged as to insure a charge of extended surface and small The mixture having been thus red temperature, whereupon the charge begins to melt. The temperature is kept up so as to maintain the charge in melted state and the molten bath is kept agitated in any convenient manner as by stirring with proper toolsso long as abundant fumes of sulfuric acid are given out.

When the fumes of sulfuric acid are observed to slack, the-liquid of the bath is tapped into appropriate vessels of cast iron or other suitable material, wherein it soon solidifies. Repeated practice can alone be relied on for determining the best moment for tapping as aforesaid, the variations in constituents and conditions being too great for any hard and fast rule, but those skilled in the art will, in the treatment of any parportion.

ticular ore, after a few operations, have no difficulty in determining from the appearance of the sulfuric acid fumes the critical moment when the required chemical 'reactions have sufliciently proceeded. The cakes resulting from the solidification aforesaid I then crush to a fine powder, in any convenient manner, and charge such powder into metallic kettles provided With linings of resistant material, for example porcelain lined kettles. Water is then poured upon the powder contained in the said kettles and means provided to raise the temperatures of the charges to the boiling point and maintain them there. This will result in the dissolving of the greater part of the charges in the boiling liquid acidulated by the sulfuric acid which has not been driven out during the aforesaid smelting together of the ore and bisulfate. Additional sulfuric acid may be added should this-appear required. This last mentioned step in my process being as stated to insure, as far as possible, the dissolving of the ingredients of the smelted product or melt, the bath must meanwhile be maintained sufliciently acid to accomplish that result, the degree of acidity required being readily determined by usual tests to suit requirements of each particular melt treated. As stated however while this procedure prolperly conducted should result in dissolving the greater part of the ingredients of the melt, there Wlll remain, particularly in the case of ilmeno-rutile ores, an undissolved pro- This in the case of said ilmenorutile ores will largely consist of the ilmenite proper, FeTiO or FeO,TiO ,which appears to be insoluble under the conditions stated. During my thus described first boil,

.the water acidulated by the sulfuric acid.

The liquid is next separated from the said insoluble residues by decanting it into another similar kettle likewise properly heated as by means of any of the usual well known devices for the purpose e. g. a current of steam passed through the boiling liquid, the

level of the boiling liquid being maintained if requlred by additions of boiling water.

The liquid being thus kept continuously boiling for a few hours, the titanium oxid, TiO will be precipitated as such and practically free from the other constituents of the charge. The heat is then turned off and the charge permitted to cool, when the precipitated titanic oxid will be found to have settled to the bottom of the kettle. The supernatant liquid is then decanted and the moist titanic oxid residuum is dried in anyconvenient manner, for instance by a usual" filter press, and finally calcined if desired, securing thus as a final product a pulverulent mass oftitanic oxid which I have in some instances obtained as pure as 98 to 99%. It is obvious that if, for some technical purposes, a still purer titanic oxid than this be required, or should in any instance the operation of my method result in a less pure product, further purification thereof may be effected by treating the product with hydrofluoric acid or other known methods for securing a chemically pure product, though this, it will be understood, is

.not usually necessary for the specific purposes to which I have hereinbefore referred. It will also be understood that should the liquid decanted be found to contain by analysis such quantity of unprecipitated titanic oxid as to. justify further treatment, it may of course be further boiled as aforesaid to insure precipitation of such residuum. i

It will be understood that the insoluble ferric and titanic constituents precipitated during my first boil as aforesaid will possess value for? certain industrial purposes in which presence of ferric constituents is not prohibitory.

I am aware that in order to produce from rutile, or ilmenite, soluble crystalline compounds of titanic acid sulfuric acid and alkali 'it has been directed that said rutile, or ilmenite, be first fritted or fused with carbonate of soda, the resulting melt thereafter. fused with acid sodium sulfate or the like, and this final melt boiled in water acidulated by sulfuric acid until its'therein soluble constituents are dissolved, the undissolved matter being separated from the resulting liquor by filtration or other'suitable means, and further boiled in the ordinary suchi could be precipitated from baths containing it in solution, by reduction of their acldity to the point of such precipitation, but this elementary chemical fact, though necessarily relied on in part by me, does not of course constitute my invention, the which embraces in its entirety an organized novel procedure whereby titanic oxidas such is, with industrial economy, separable from materials such as ores in which it is entangled with ilmenite, iron oxids and other undesired substances, my said procedure enabling the manufacturer to dispense with agents and steps hitherto believed essential,

and 'to secure 'at less expense a purer and better titanic oxid concentrate than hitherto, as I believe, attainable.

I am also aware that it has been asserted that titanic oxid can be precipitated from sulfuric acid solutions thereof by boiling them with additions however of a deacidifying reagent, or alkaline substance, such as carbonate of soda, and do not wish to beunderstood as claiming anything involving such procedure, my invention being distinguishable therefrom in that my solution is prepared only as above stated, and in consequence the titanic acid is therein precipitable without aid of any such reagents, provided the concentration of the solution be kept constant as by suitable additions of water.

What I claim as new and desire to secure by Letters Patent is the following, viz

1. The method of obtaining titanic oxid (TiO from ore containing therewith intermixed ilmenite molecules (FeTiO .FeO,TiOf1), which comprises melting such ore toget er with bisulfate of soda; iling the resulting melt in water with addition of acid until titanic oxid is dissolved; withdrawing the resulting solution from therein undissolved ilmenite molecules; thereafter again boiling the solution with additions of water suflicient to maintain its concentration.

until titanic oxid is precipitated; withdrawing from the solution the precipitated titanic oxid; and drying it.

2. The method of obtaining titanic oxid (TiO. from ore containing therewith intermixed ilmenite molecules (FeTiO FeO,TiO,), which comprises melting such ore together with bisulfate'of soda; boiling the resulting melt in water with addition of acid until titanic oxid is dissolved; withdrawing the resulting solution from therein undissolved ilmenite molecules; thereafter again boiling the solution with additions of water suflicient to maintain its concentration until titanic oxid is precipitated; withdrawing from the solution the precipitated titanic oxid; drying it; and calcining it.

- AUGUSTE J. ROSSI.

Witnesses:

WALTER D. EDMONDS, PHILIP O. PECK. 

